Sulfuric acid esters and a process of making same



Patented Dec. 30, 1947 UNITED STATES PATENT OFFICE,

SULFURIC ACIl) ESTERS AND A PROCESS OF MAKING SAME Jakob Bindler and Hans Schliipfer, Basel, Switzerland, assignors to J. R. Geigy A. G., Basel,

Switzerland No Drawing.

Application May 11, 1944, Serial No. 535,198. In Switzerland May 12, 1943 8 Claims. (Cl. 260-401) 1 It has been found that by condensation of compounds which contain at least once the atom grouping and a high molecular aliphatic radical with at least 12 carbon atoms, with alkylene oxides which are capable of addition in the molar ratio of 1 to at least 2 and by sulfonation of the hydroxyalkyl compounds valuable new capillary-- guanamines (triazines, etc.) the same having al-,

ready been described in the patent literature. As alkylene compounds there may be mentioned especially ethylene oxide, but also d-propylene oxide, isobutylene oxide, alkyl ethylene oxides, glycide,- epichlorohydrine and so on. The transformation into sulfuric acid esters, as well as the hydroxyalkylation of the high molecular substituted starting products is carried out according to known methods.

The present invention will now be described by way of examples, without being limited thereto. The parts are by weight.

Example 1 35 parts of stearoyl cyanoguanidine of the formula made from stearic acid and dicyanodiamide, are mixed with 02 part of sodium ethylate and at 140-150 C. 22. parts of glycide are slowly dropped thereinto. under a vigorous development of heat. The clear, bright brown melt is stirred for still further 14 hours at the same temperature until a homogeneous mixture has resulted. After cooling the condensation product is obtained in form of a brown waxy mass.

15 parts of this compound are dissolved at 60 C. in 20 parts of. monohydrate and sulfonated at 20 C. with 20 parts of chlorosulfonic acid until The reaction takes place ing power is also very good.

water-solubility has been reached. The sulfonation mass is then poured onto ice and, after separation of the aqueous layer, neutralized by means of caustic soda lye. The final product forms a bright, water-soluble powder having very good capillary-active properties.

Example 2 20 parts of a condensation product of the probable formula 0.111130omngnngnmmmon NE NH obtainable in a known manner from dicyanodiamide, cocoa fatty acid and ethanol amine, are condensed with the double molar quantity of glycide in the manner indicated in Example 1, then dissolved in 40 parts of monohydrate and sulfonated at 10-15 C. with 40 parts of 26% oleum. After addition of the whole quantity of oleum stirring is continued at room temperature until a test sample has become .clearly soluble in water. This being the case, the mixture is poured onto ice, neutralized and, after addition of common salt, the final product is extracted with isopropyl alcohol. After having dried the extract and distilled the extracting agent one obtains a bright powder which is easilyv soluble in water and possesses very excellent properties as washing and wetting agents as well as as limesoap solvent and emulsifying agent.

Example 3 23 parts of the compound prepared by methylation of w-phenyl-w'-stearoyl biguanide (22 parts of the biguanide compound are dissolved in 250 parts of chlorobenzene, treated with 6.3 parts of dimethyl sulfate and 5.5 parts of sodium carbonate and heated during 6 hours to l00-110 0., then the inorganic salts and the solvent are removed, whereby a bright brown, fatty mass is obtained) are condensed with glycide in the manner described in Example 1. Thus a waxy mass is obtained.

' 10 parts of this condensation product are dissolved in 20 parts .of monohydrate and dropwise treated at 0-10 C. with 10 parts of 26% oleum. Stirring is continued at room temperature until a test sample is soluble in a dilute sodium carbonate solution. The working up is carried out as described in Example 1. 'I'heiinal product possesses good properties for stripping purposes for vat dyestuffs.

Its foam- 3 Example 4 32.5 parts of cocoa fatty acid hydroxyethyl biguanide of the formula CnHn.CO.NH.9.NH.fi.NH-C:BQOH

NE NH are condensed in the usual manner with 9 parts of ethylene oxide, then sulfonated and worked up according to the method indicated in Example d1- powder with good capillary-active properties.

Instead of glycide or ethylene oxide used in the above examples, the other reactive alkylene oxides mentioned in the general part of this specification, such as e-propylene oxide, isobutylene oxide, epichlorohydrine and the like, may quite well be used, without changing substantially the properties of the final products. By increasing the quantity of hydroxyalkylating agents mentioned in the examples, for instance by using the one and a half-, two-, threeor fourfold quantity, etc, compounds with similar properties are obtained.

What we claim is:

1. Process for the manufacture of a sulfuric acid ester which comprises hydroxyalkylating a compound of the formula wherein R-CO represents the radical of a fatty carboxylic acid with 12 to 18 carbon atoms and X represents a member selected from the group consisting of cyano and amidino radicals, with 2 to 12 molar portions of an alkylene oxide, and sulfonating the so-obtained hydroxyalkylated compound.

2. Process for the manufacture of a sulfuric acid ester, which comprises hydroxyalkylating 1 mole of stearoyl cyano guanidine of the formula cnuaconnf rnncn with three moles of glycide and sulfonating the CIIHSCO-NH-(IfNH.fi.NH-CZH|OH wherein C11H23CO means the radical of cocoa fatty acid, with substantially 2 moles of ethylene The final product thus obtained is a bright oxide and sultonating the so-obtained hydroxyalkylated compound.

5. A sulionic acid ester containing the atom ercunins ii a wherein R-CO represents the radical of a fatty carboxylic acid with 12 to 18 carbon atoms, from the hydroiwalkylation of a compound of the formula CuHa.C0.NH.(fi.NH.CN

with three moles of glycide and sulfonating the so-obtained hydroxyalkylated compound.

7. The sulfonic acid ester from the hydroxyalkylatlon of 1 mole of the condensation product of dlcyanodiamide with cocoa fatty acid and ethanolamine which condensation product has i the probable formula CuHnCO.NH.C.NH.C.NH.C2H4OH NH NH wherein C11H23CO means the radical of cocoa fatty acid, with substantially 2 moles of glycide and sulfonating' the so -obtained hydroxyalkylated compound.

8. The sulfonic acid ester from the hydroxyethylation of one mole of cocoa fatty acid-hydroxyethyl-biguanide of the probable formula CnHnCO,NH.(i3.NH.lCl.NH.C2H40H NE NH wherein CnHzCO means the radical of cocoa fatty acid, with substantially 2 moles of ethylene oxide and sulfonating the so-obtained hydroxyalkylated compound.

JAKOB BINDLE'R. HANS REFERENCES crrnn The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,002,613 Orthner et al May 28, 1935 2,008,649 Ulrich et al. 'July 16, 1935 2,098,551 Orthner et a] Nov. 9, 1937 2,187,823 Ulrich et al. Jan.- 23, 1940 2,214,352 Schoeller et a1. Sept. 10, 1940 2,315,765 Bindler Apr. 6, 1943 

